JP2677041B2 - Semiconductor porcelain with positive temperature coefficient of resistance - Google Patents
Semiconductor porcelain with positive temperature coefficient of resistanceInfo
- Publication number
- JP2677041B2 JP2677041B2 JP3104763A JP10476391A JP2677041B2 JP 2677041 B2 JP2677041 B2 JP 2677041B2 JP 3104763 A JP3104763 A JP 3104763A JP 10476391 A JP10476391 A JP 10476391A JP 2677041 B2 JP2677041 B2 JP 2677041B2
- Authority
- JP
- Japan
- Prior art keywords
- resistance
- temperature coefficient
- content
- total content
- semiconductor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000004065 semiconductor Substances 0.000 title claims description 43
- 229910052573 porcelain Inorganic materials 0.000 title claims description 23
- 239000000460 chlorine Substances 0.000 claims description 35
- 229910052794 bromium Inorganic materials 0.000 claims description 32
- 229910052801 chlorine Inorganic materials 0.000 claims description 32
- 229910052731 fluorine Inorganic materials 0.000 claims description 32
- 239000000919 ceramic Substances 0.000 claims description 18
- 229910002113 barium titanate Inorganic materials 0.000 claims description 10
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- -1 fluorine (F) Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Apparatuses And Processes For Manufacturing Resistors (AREA)
- Thermistors And Varistors (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、正の抵抗温度係数を
有するチタン酸バリウム（ＢａＴｉＯ3）系半導体磁器
に関し、詳しくは、その室温比抵抗の低減に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to barium titanate (BaTiO 3 ) based semiconductor ceramics having a positive temperature coefficient of resistance, and more particularly to reduction of room temperature specific resistance thereof.
【０００２】[0002]
【従来の技術】近年、大きな正の抵抗温度係数を有する
チタン酸バリウム（ＢａＴｉＯ3）系半導体磁器が開発
されており、この半導体磁器は、キュリー温度を越える
と抵抗値が急激に増大して、通過する電流量を減少させ
ることから、回路の過電流保護用や、テレビ受像機のブ
ラウン管枠の消磁用など種々の用途に広く用いられてい
る。一方、このチタン酸バリウム系半導体磁器を用いた
素子をさらに大電流化し、小型化するために、半導体磁
器の室温比抵抗をこれまで以上に低減することが要求さ
れている。2. Description of the Related Art In recent years, barium titanate (BaTiO 3 ) based semiconductor porcelain having a large positive temperature coefficient of resistance has been developed, and the resistance of this semiconductor porcelain rapidly increases when the Curie temperature is exceeded. Since it reduces the amount of current passing through, it is widely used for various purposes such as circuit overcurrent protection and degaussing of the cathode ray tube frame of a television receiver. On the other hand, in order to further increase the current and reduce the size of the element using the barium titanate-based semiconductor ceramic, it is required to further reduce the room temperature specific resistance of the semiconductor ceramic.
【０００３】正の抵抗温度係数を有する半導体磁器の室
温比抵抗の低減に関しては、Ｆｅ，Ｃｒ，Ｎａ，Ｋなど
の微量成分（不純物）の混入を抑制することが重要であ
り、これらの不純物の混入を抑制防止することにより、
室温比抵抗を低減する方法が知られている。そして、例
えば，Ｆｅについては、０．００１％レベルでの混入で
抵抗値が著しく上昇すると報告されている（センサ技
術、１９９０年４月号、ｐ４４）。In order to reduce the room temperature specific resistance of a semiconductor ceramic having a positive temperature coefficient of resistance, it is important to suppress the mixing of trace components (impurities) such as Fe, Cr, Na and K. By suppressing and preventing contamination,
A method for reducing the room temperature specific resistance is known. Then, for example, it has been reported that the resistance value of Fe increases remarkably when it is mixed at the 0.001% level (sensor technology, April 1990 issue, p44).
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記従来の方
法では、室温比抵抗をある程度は低減できるものの、従
来着目していたＦｅ，Ｃｒ，Ｎａ，Ｋなどの元素の混入
量を低減するのみでは、室温比抵抗の低減効果は必ずし
も十分ではなく、室温比抵抗のさらに低い正の抵抗温度
係数を有する半導体磁器が望まれていた。However, although the above-mentioned conventional method can reduce the room temperature resistivity to some extent, it does not only reduce the mixing amount of elements such as Fe, Cr, Na, and K, which has been conventionally focused. However, the effect of reducing the room temperature resistivity is not always sufficient, and a semiconductor ceramic having a positive temperature coefficient of resistance with a lower room temperature resistivity has been desired.
【０００５】この発明は、上記問題点を解決するもので
あり、Ｆｅ，Ｃｒ，Ｎａ，Ｋなどの含有量を減少させる
ことにより室温比抵抗を低減した従来の半導体磁器より
もさらに室温比抵抗の低い正の抵抗温度係数を有する半
導体磁器を提供することを目的とする。The present invention solves the above problems and has a room temperature resistivity higher than that of the conventional semiconductor porcelain in which the room temperature resistivity is reduced by reducing the contents of Fe, Cr, Na, K and the like. An object is to provide a semiconductor porcelain having a low positive temperature coefficient of resistance.
【０００６】[0006]
【課題を解決するための手段及び作用】上記目的を達成
するために、この発明の半導体磁器は、正の抵抗温度係
数を有するチタン酸バリウム系半導体磁器のフッ素，塩
素，及び臭素の含有量の合計を０．０１原子％（at％)
以下にしたことを特徴とする。In order to achieve the above object, the semiconductor porcelain of the present invention has a fluorine, chlorine, and bromine content of barium titanate-based semiconductor porcelain having a positive temperature coefficient of resistance. Total 0.01 atom% (at%)
It is characterized by the following.
【０００７】なお、この発明の正の抵抗温度係数を有す
る半導体磁器には、０．０１原子％（at％）以下のＭｎ
を含有させることができる。The semiconductor ceramic having a positive temperature coefficient of resistance according to the present invention has a Mn content of 0.01 atomic% (at%) or less.
Can be included.
【０００８】この発明の正の抵抗温度係数を有する半導
体磁器は、室温比抵抗をさらに低減することを目的とし
て、半導体磁器中の微量不純物を分析し、その影響を綿
密に検討することにより発明されるに至ったものであ
る。すなわち、不純物として、従来より注目されていた
Ｆｅ，Ｃｒ，Ｎａ，Ｋなどの陽イオン以外にも、陰イオ
ンであるフッ素（Ｆ）、塩素（Ｃｌ）、臭素（Ｂｒ）が
半導体磁器の低抵抗化を阻害しており、これらの元素の
含有量の合計を０．０１原子％以下にすることにより、
正の抵抗温度係数を有するチタン酸バリウム系半導体磁
器をさらに低抵抗化することが可能であることを知り、
この発明を完成したものである。The semiconductor porcelain having a positive temperature coefficient of resistance according to the present invention was invented by analyzing a trace amount of impurities in the semiconductor porcelain and carefully studying the influence thereof for the purpose of further reducing the room temperature resistivity. It has come to the end. That is, as impurities, in addition to cations such as Fe, Cr, Na, and K, which have been attracting attention in the past, anions such as fluorine (F), chlorine (Cl), and bromine (Br) have a low resistance in semiconductor porcelain. Is suppressed, and the total content of these elements is set to 0.01 atomic% or less,
Knowing that it is possible to further reduce the resistance of barium titanate-based semiconductor porcelain having a positive temperature coefficient of resistance,
The present invention has been completed.
【０００９】また、チタン酸バリウム系半導体磁器で
は、抵抗温度係数を高めるために、Ｍｎを添加すること
があるが、上述したＦ，Ｃｌ，Ｂｒの合計含有量を低減
させることによる比抵抗低減の効果は、Ｍｎ添加量が
０．０１原子％以下の場合には特に顕著であり、Ｍｎ添
加量をそれ以上にした場合には、Ｍｎの添加による半導
体磁器の高抵抗化のために、Ｆ，Ｃｌ，Ｂｒの合計含有
量を減少させることによる低抵抗化の効果が相殺され、
全体としては低抵抗化の効果が小さくなる。Further, in barium titanate-based semiconductor ceramics, Mn may be added in order to increase the temperature coefficient of resistance, but the specific resistance can be reduced by reducing the total content of F, Cl and Br described above. The effect is particularly remarkable when the added amount of Mn is 0.01 atomic% or less, and when the added amount of Mn is more than that, in order to increase the resistance of the semiconductor ceramics by the addition of Mn, F, The effect of lowering the resistance by reducing the total content of Cl and Br is offset,
As a whole, the effect of lowering the resistance becomes smaller.
【００１０】[0010]
【実施例】以下に、実施例を示してこの発明の特徴をさ
らに詳細に説明する。EXAMPLES The features of the present invention will be described in more detail below with reference to examples.
【００１１】（実施例１）ＢａＣＯ3，ＢａＣｌ2，Ｔｉ
Ｏ2，ＳｒＣＯ3，ＣａＣＯ3，Ｌａ2Ｏ3，ＭｎＯ2，Ｓｉ
Ｏ2を下記の式(1)で表される組成になるように調合し
た。 （Ｂａ0.846Ｓｒ0.05Ｃａ0.10Ｌａ0.004）（Ｔｉ(1-X)ＭｎX）Ｏ3＋０．００１ ＳｉＯ2（ただし、Ｘ＝０〜０．０１６） ……(1)Example 1 BaCO 3 , BaCl 2 , Ti
O 2, SrCO 3, CaCO 3 , La 2 O 3, MnO 2, Si
O 2 was blended so as to have a composition represented by the following formula (1). (Ba 0.846 Sr 0.05 Ca 0.10 La 0.004 ) (Ti (1-X) Mn X ) O 3 +0.001 SiO 2 (where X = 0 to 0.016) (1)
【００１２】なお、上記原料の調合の際に、焼成後の半
導体磁器中のＣｌ含有量を変化させるため、ＢａＣＯ3
に対するＢａＣｌ2の割合を０〜１０％の範囲で変え
た。また、ＢａＣｌ2以外の原料は、Ｆ，Ｃｌ，Ｂｒの
含有量の合計が、０．００１原子％以下のものを使用す
るとともに、フッ素系樹脂、塩化ビニル、汗など、Ｆ，
Ｃｌ，Ｂｒの混入要因となる物質が混入しないように細
心の注意を払った。In the preparation of the above raw materials, the Ba content of BaCO 3 is changed in order to change the Cl content in the semiconductor porcelain after firing.
The ratio of BaCl 2 with respect to was varied in the range of 0-10%. As the raw materials other than BaCl 2 , those having a total content of F, Cl and Br of 0.001 atomic% or less are used, and fluorine resin, vinyl chloride, sweat, etc.
Great care was taken not to mix in substances that could become the contaminating factor of Cl and Br.
【００１３】この調合粉をエタノール及びジルコニアボ
ールとともにポリエチレン製ポットに入れて５時間粉砕
混合した後、蒸発乾燥し、１１００℃で２時間仮焼し
た。この仮焼粉に酢酸ビニル系のバインダーを５重量％
添加して混合した後乾燥し、プレス成形機により直径１
７mm、厚さ３mmの円板状の成形体を作成した。そして、
この成形体を、１３５０℃の温度で１時間、大気中で焼
成し、焼成体（半導体磁器）を得た。それから、この半
導体磁器の両主面に、Ｉｎ−Ｇａ合金を塗布して電極を
形成し、これを特性測定用の試料とした。This blended powder was put in a polyethylene pot together with ethanol and zirconia balls, pulverized and mixed for 5 hours, evaporated to dryness, and calcined at 1100 ° C. for 2 hours. Add 5% by weight of vinyl acetate binder to this calcined powder.
Add and mix, dry, and press press to obtain a diameter of 1
A disk-shaped molded body having a thickness of 7 mm and a thickness of 3 mm was prepared. And
This molded body was fired in the air at a temperature of 1350 ° C. for 1 hour to obtain a fired body (semiconductor porcelain). Then, an In—Ga alloy was applied to both main surfaces of the semiconductor porcelain to form electrodes, which were used as samples for characteristic measurement.
【００１４】なお、上記実施例１においては、各試料
（半導体磁器）中のＦとＢｒの含有量をそれぞれ０．０
０２原子％及び０．００１原子％一定とし、Ｃｌ含有量
のみを変化させた。In Example 1, the contents of F and Br in each sample (semiconductor porcelain) were 0.0.
Only 02 content% and 0.001 content% were fixed, and only the Cl content was changed.
【００１５】図１に、上記実施例１の各試料について
の、Ｆ，Ｃｌ，Ｂｒの合計含有量と室温比抵抗との関係
を示す。図１より、Ｆ，Ｃｌ，Ｂｒの合計含有量が少な
いほど比抵抗が低く、特にＦ，Ｃｌ，Ｂｒの合計含有量
が０．０１原子％以下では、比抵抗が著しく低下するこ
とがわかる。また、比抵抗の低下は、Ｍｎ含有量が０．
０１原子％以下のときに顕著であり、Ｍｎ含有量が０．
０１６原子％になると、Ｍｎの添加による半導体磁器の
高抵抗化のため、Ｆ，Ｃｌ，Ｂｒの合計含有量を減少さ
せたことによる低抵抗化の効果が打ち消され、全体とし
ては低抵抗化の効果が小さくなることがわかる。FIG. 1 shows the relationship between the total content of F, Cl and Br and the room temperature resistivity for each sample of Example 1 above. From FIG. 1, it can be seen that the smaller the total content of F, Cl, Br is, the lower the specific resistance is. Particularly, when the total content of F, Cl, Br is 0.01 atomic% or less, the specific resistance is remarkably lowered. In addition, the decrease in the specific resistance is due to the Mn content being 0.
It is remarkable when the content is 01 atomic% or less, and the Mn content is 0.
When the content is 016 atom%, the resistance of the semiconductor ceramics is increased by the addition of Mn, so that the effect of lowering the resistance by reducing the total content of F, Cl, Br is canceled out, and the resistance of the whole is lowered. It can be seen that the effect becomes smaller.
【００１６】また、図２に、上記実施例１の各試料につ
いてのＦ，Ｃｌ，Ｂｒの合計含有量と抵抗温度係数との
関係を示す。図２より、抵抗温度係数はＦ，Ｃｌ，Ｂｒ
の合計含有量を減少させても殆ど低下しないことがわか
る。なお、Ｍｎ含有量が多いほど、抵抗温度係数が高く
なっており、室温比抵抗が高くならない範囲（Ｍｎ含有
量０．０１原子％以下）でＭｎを含有させることが望ま
しいことがわかる。FIG. 2 shows the relationship between the total content of F, Cl and Br and the temperature coefficient of resistance for each sample of Example 1 above. From Fig. 2, the temperature coefficient of resistance is F, Cl, Br.
It can be seen that even if the total content of is decreased, it hardly decreases. It should be noted that the higher the Mn content, the higher the temperature coefficient of resistance, and it is understood that it is desirable to contain Mn in a range where the room temperature specific resistance does not increase (Mn content 0.01 atomic% or less).
【００１７】なお、抵抗温度係数は、下記の式(2)によ
り算出した値である。 抵抗温度係数＝｛２．３０３／（Ｔ2−Ｔ1）｝×１００ ……(2) Ｔ1＝抵抗が室温抵抗の１０倍になる温度 Ｔ2＝抵抗が室温抵抗の１００倍になる温度The resistance temperature coefficient is a value calculated by the following equation (2). Temperature coefficient of resistance = {2.303 / (T 2 −T 1 )} × 100 (2) T 1 = temperature at which resistance becomes 10 times room temperature resistance T 2 = temperature at which resistance becomes 100 times room temperature resistance
【００１８】（実施例２）原料の調合時にＢａ原料とし
てＢａＣＯ3を用いたこと及び、バインダーを混合しこ
れを乾燥した後、フッ素樹脂（テフロン（商品名））微
粒子を添加し、遊星ミルで乾式混合することにより焼成
後の残留Ｆ量を制御したこと以外は上記実施例１と同様
の方法で半導体磁器を作成した。(Example 2) BaCO 3 was used as a Ba raw material at the time of preparing raw materials, and a binder was mixed and dried. A semiconductor porcelain was prepared in the same manner as in Example 1 above, except that the amount of residual F after firing was controlled by dry mixing.
【００１９】なお、この実施例２においては、試料（半
導体磁器）中のＣｌとＢｒの含有量をそれぞれ０．００
３原子％及び０．００１原子％一定とし、Ｆの含有量の
みを変化させた。In Example 2, the contents of Cl and Br in the sample (semiconductor porcelain) were each 0.00
Only 3% by atom and 0.001% by atom were kept constant, and only the F content was changed.
【００２０】図３に、上記実施例２の各試料について
の、Ｆ，Ｃｌ，Ｂｒの合計含有量と室温比抵抗との関係
を示す。図３より、Ｆ，Ｃｌ，Ｂｒの合計含有量が少な
いほど比抵抗が低く、特にＦ，Ｃｌ，Ｂｒの合計含有量
が０．０１原子％以下では、比抵抗が著しく低下するこ
とがわかる。また、比抵抗の低下は、Ｍｎ含有量が０．
０１原子％以下のときに顕著である。FIG. 3 shows the relationship between the total content of F, Cl and Br and the room temperature specific resistance for each sample of Example 2 described above. From FIG. 3, it can be seen that the smaller the total content of F, Cl and Br, the lower the specific resistance, and in particular, the specific resistance is remarkably lowered when the total content of F, Cl and Br is 0.01 atomic% or less. In addition, the decrease in the specific resistance is due to the Mn content being 0.
It is remarkable when the content is 01 atomic% or less.
【００２１】また、図４に、上記実施例２の各試料につ
いてのＦ，Ｃｌ，Ｂｒの合計含有量と抵抗温度係数との
関係を示す。図４より、抵抗温度係数はＦ，Ｃｌ，Ｂｒ
の合計含有量を減少させても殆ど変化しないことがわか
る。FIG. 4 shows the relationship between the total content of F, Cl and Br and the temperature coefficient of resistance for each sample of Example 2 described above. From FIG. 4, the temperature coefficient of resistance is F, Cl, Br.
It can be seen that there is almost no change even if the total content of is reduced.
【００２２】（実施例３）仮焼後にバインダーを混合
し、これを乾燥した後、ＢｒＣ6Ｈ4ＮＨＣＯＣＨ3を添
加し、遊星ミルで乾式混合することにより焼成後の残留
Ｂｒ量を制御したこと以外は上記実施例２と同様の方法
で半導体磁器を作成した。Example 3 A binder was mixed after calcination, dried, BrC 6 H 4 NHCOCH 3 was added, and the amount of residual Br after firing was controlled by dry mixing with a planetary mill. A semiconductor porcelain was prepared in the same manner as in Example 2 except for the above.
【００２３】なお、上記実施例３においては、試料（半
導体磁器）中のＦとＣｌの含有量を各々０．００２原子
％及び０．００３原子％一定とし、Ｂｒの含有量のみを
変化させた。In Example 3, the contents of F and Cl in the sample (semiconductor porcelain) were kept constant at 0.002 atom% and 0.003 atom%, respectively, and only the content of Br was changed. .
【００２４】図５に、上記実施例３の各試料について
の、Ｆ，Ｃｌ，Ｂｒの合計含有量と室温比抵抗との関係
を示す。図５より、Ｆ，Ｃｌ，Ｂｒの合計含有量が少な
いほど比抵抗が低く、特にＦ，Ｃｌ，Ｂｒの合計含有量
が０．０１原子％以下では、比抵抗の顕著な低下が認め
られ、さらに、比抵抗の低下は、Ｍｎ含有量が０．０１
原子％以下のときに顕著であることがわかる。FIG. 5 shows the relationship between the total content of F, Cl and Br and the room temperature resistivity for each sample of the above Example 3. From FIG. 5, the lower the total content of F, Cl, Br, the lower the specific resistance. Particularly, when the total content of F, Cl, Br is 0.01 atomic% or less, a remarkable decrease in the specific resistance is recognized. Further, the decrease in the specific resistance is due to the Mn content being 0.01
It can be seen that it is remarkable when the content is atomic% or less.
【００２５】また、図６に、上記実施例３の各試料につ
いてのＦ，Ｃｌ，Ｂｒの合計含有量と抵抗温度係数との
関係を示す。図６より、抵抗温度係数はＦ，Ｃｌ，Ｂｒ
の合計含有量を減少させても殆ど低下しないことがわか
る。FIG. 6 shows the relationship between the total content of F, Cl and Br and the temperature coefficient of resistance for each sample of Example 3 above. From FIG. 6, the temperature coefficient of resistance is F, Cl, Br.
It can be seen that even if the total content of is decreased, it hardly decreases.
【００２６】なお、この発明の正の抵抗温度係数を有す
る半導体磁器の主成分であるチタン酸バリウム系半導体
材料としては、半導体化剤としてＹ，Ｌａなどの希土類
元素やＮｂ，Ｓｂその他の元素を含有させたものや、Ｂ
ａの一部をＳｒ，Ｐｂ，Ｃａなどで置換したものなど種
々のチタン酸バリウム系材料を用いることが可能であ
る。As the barium titanate-based semiconductor material which is the main component of the semiconductor porcelain having a positive temperature coefficient of resistance according to the present invention, rare earth elements such as Y and La and Nb, Sb and other elements are used as a semiconductor agent. B contained
It is possible to use various barium titanate-based materials such as those obtained by substituting a part of a with Sr, Pb, Ca or the like.
【００２７】[0027]
【発明の効果】上述のように、この発明によれば、チタ
ン酸バリウム系半導体磁器材料のＦ，Ｃｌ，Ｂｒの合計
含有量を０．０１原子％以下にしているので、正の抵抗
温度係数を有する半導体磁器の抵抗温度係数を劣化させ
ることなく、室温比抵抗を大幅に低減することが可能に
なり、素子の大電流化、小型化を実現することができ
る。As described above, according to the present invention, the total content of F, Cl and Br in the barium titanate-based semiconductor ceramic material is set to 0.01 atom% or less. It is possible to significantly reduce the room temperature resistivity without deteriorating the temperature coefficient of resistance of the semiconductor porcelain having, and it is possible to increase the current and size of the element.
【００２８】また、この発明によれば、Ｍｎを０．０１
原子％まで含有させることが可能であり、室温比抵抗と
抵抗温度係数の両方に優れた正の抵抗温度係数を有する
半導体磁器を得ることができる。According to the present invention, Mn is 0.01
It is possible to contain up to atomic%, and it is possible to obtain a semiconductor ceramic having a positive temperature coefficient of resistance which is excellent in both room temperature resistivity and temperature coefficient of resistance.
【図１】実施例１の半導体磁器のＦ，Ｃｌ，Ｂｒの合計
含有量と室温比抵抗との関係を示す線図である。FIG. 1 is a diagram showing the relationship between the total content of F, Cl, Br in a semiconductor ceramic of Example 1 and room temperature specific resistance.
【図２】実施例１の半導体磁器のＦ，Ｃｌ，Ｂｒの合計
含有量と抵抗温度係数との関係を示す線図である。FIG. 2 is a diagram showing the relationship between the total content of F, Cl, Br in the semiconductor ceramic of Example 1 and the temperature coefficient of resistance.
【図３】実施例２の半導体磁器のＦ，Ｃｌ，Ｂｒの合計
含有量と室温比抵抗との関係を示す線図である。FIG. 3 is a diagram showing the relationship between the total content of F, Cl, Br in the semiconductor ceramic of Example 2 and the room temperature specific resistance.
【図４】実施例２の半導体磁器のＦ，Ｃｌ，Ｂｒの合計
含有量と抵抗温度係数との関係を示す線図である。FIG. 4 is a diagram showing the relationship between the total content of F, Cl and Br and the temperature coefficient of resistance of the semiconductor ceramic of Example 2.
【図５】実施例３の半導体磁器のＦ，Ｃｌ，Ｂｒの合計
含有量と室温比抵抗との関係を示す線図である。FIG. 5 is a graph showing the relationship between the total content of F, Cl, Br and the room temperature specific resistance of the semiconductor ceramic of Example 3.
【図６】実施例３の半導体磁器のＦ，Ｃｌ，Ｂｒの合計
含有量と抵抗温度係数との関係を示す線図である。FIG. 6 is a graph showing the relationship between the total content of F, Cl and Br in the semiconductor ceramic of Example 3 and the temperature coefficient of resistance.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭58−70502（ＪＰ，Ａ) 特開 平４−188601（ＪＰ，Ａ) 特開 平３−218966（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-58-70502 (JP, A) JP-A-4-188601 (JP, A) JP-A-3-218966 (JP, A)
Claims (2)
ウム系半導体磁器において、該半導体磁器のフッ素，塩
素，及び臭素の含有量の合計が０．０１原子％以下であ
ることを特徴とする正の抵抗温度係数を有する半導体磁
器。1. A barium titanate-based semiconductor ceramic having a positive temperature coefficient of resistance, wherein the total content of fluorine, chlorine, and bromine in the semiconductor ceramic is 0.01 atomic% or less. Porcelain having a temperature coefficient of resistance of.
ことを特徴とする請求項１記載の正の抵抗温度係数を有
する半導体磁器。2. The semiconductor porcelain having a positive temperature coefficient of resistance according to claim 1, wherein the Mn content is 0.01 atomic% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3104763A JP2677041B2 (en) | 1991-04-09 | 1991-04-09 | Semiconductor porcelain with positive temperature coefficient of resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3104763A JP2677041B2 (en) | 1991-04-09 | 1991-04-09 | Semiconductor porcelain with positive temperature coefficient of resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04311003A JPH04311003A (en) | 1992-11-02 |
| JP2677041B2 true JP2677041B2 (en) | 1997-11-17 |
Family
ID=14389525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3104763A Expired - Lifetime JP2677041B2 (en) | 1991-04-09 | 1991-04-09 | Semiconductor porcelain with positive temperature coefficient of resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2677041B2 (en) |
-
1991
- 1991-04-09 JP JP3104763A patent/JP2677041B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04311003A (en) | 1992-11-02 |
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